Cracking hydrocarbons in the presence of bromine-containing terpenic compounds



Patented May 11, 1948 UNITED STATES PATENT OFFICE 2,441,142 V CRACKINGnrnaocaanons IN THE PRES- ENCE F PENIC COMPOUNDS Hillis 0. Folkins,Skokie, 111., assignor to The Pure Oil Company, Chicago, Ill, acorporation of Ohio BROMlNE-CONTAINI'N G TER- No Drawing. ApplicationDecember 14, 1944, Serial No. 568,197

14 Claims. (ca. 196-52) of hydrocarbons when mixed in small amounts withthe hydrocarbons undergoing decomposition.

One of the objects of this invention is to provide an improved methodfor converting hydrocarbons into lower boiling hydrocarbons and/or intohydrocarbons of less saturation.

Another object of the invention is to accelerate the rate of cracking ofhydrocarbons.

Still another object of the invention is to provide a method forincreasing the yield of cracked hydrocarbons in conventional typecracking operations.

Still a further object of the invention is to produce motor fuel ofincreased octane number.

Other objects of the invention will become manifest from the followingdescription.

In accordance with my invention, hydrocarbons are mixed with a smallamount of a terpene or camphor or a mixture thereof having one or morehalogen atoms in the molecule. Compounds having more than one halogenatom in the molecule are preferred. As examples of halogenated terpenesand camphor type compounds which may be used in the invention are:

d-Limonene tetrabromide Dlpentene tetrabromide Bromo-menthone 1,4,8trlbromo p-menthane d-Carvone hydrobromide d-Bromocamphor2-bromocamphane-3 carboxylic acid u-bromocamphene BromoienchoneBromoepicamphor Bromonitrocamphane Born'yl bromide ChlorobromocamphanePlnene dibromide In addition to the halogenated terpenes and camphors,halogenated derivatives thereof such as esters, ethers and amino, nltro,alkyl, aryl and aralkyl derivatives in which the aforesaid groups aresubstituted for one or more hydrogen atoms in the molecule may be used.The brominated terpenes and camphors and derivatives thereof give goodresults when used in amounts of approximately .05 to 5% by weight ofhydrocarbons' undergoing cracking, although smaller amounts may be used.I prefer not to use in 8X";

cess of 3% by weight, since amounts below 3% provide satisfactoryacceleration of the cracking reaction without causing the presence of objectlonable amounts of undesirable compounds in the resulting product.Generally speaking, 1%

or less of the brominated compound is adequate.-

Instead of using pure halogenated terpenes and camphors, or derivativesthereof, I may .use substances rlch 131- any of the aforesaid compoundsand halogenatc the substances. As an example, brominated turpentineprovides a satisfactory sensitizer since turpentine is largely alpha andbeta, pinene.

Although the aforesaid sensitizers are primarily useful in crackinghydrocarbon oils boiling above the gasoline boiling range, in order toproduce gasoline, or in cracking gasoline-boiling range hydrocarbons toproduce gasoline of higher antiknock value, the invention is directedalso to the cracking of hydrocarbon gases such as propane or butane inorder to produce unsaturated hydrocarbons.

Sensitizers, in accordance with my invention, are useful in conventionalthermal cracking processes at atmospheric, sub-atmospheric orsuperatmospheric pressure. Cracking of hydrocarbon oils and gases maybecarried out within the t'emperature range of apfirbximately 650 to2000 F., depending on the nature of the charging stock and the type ofproduct desired. Where cracking of hydrocarbon oils to gasoline ispracticed, the temperature may range from approximately 650 to 1200 F.When cracking gases or oils in order to form aromatics, temperatures ofapproximately 1000-1500 F. may be resorted to. Where it is desired tocrack hydrocarbon oils and gases to butadiene, a temperature ofapproximately 1300 to 1600" F. may be used. Where cracking of oils orgases to low molecular weight gaseous hydrocarbons is desired,temperatures of the order of 1500 to 2000 F. may be used.

From the table it will be seen that without any sensitizer being present(run No. 24-G) the yield of gasoline (liquid below 400 F.) was 11.2% andthe total yield of products below 400 F. was 16.7%.

When 0.1% by weight of bromine was present (run No. 28-G), the yield ofgasoline was 13.1% and the total yield of products boiling below 400 F.was 21.6

Run No. 23-G made with 0.1% by weight of d-bromocamphor as sensitizergave a gasoline yield of 14.8% and a total yield of products boilingbelow 400 F. of 22.2%. Thus, d-bromocamphor not only excels bromine on aweight for weight basis, but considering the small amount of brominepresent in the compound, the compound is remarkably effective.

Run No. 22-G made with 0.5% by weight of l d-bromocamphor produced agasoline yield of 17.2% by weight, and run No. 21-G using 1.0% by weightof d-bromocamphor produced a gasoline yield of 22.3%, almost twice theyield obtained without any sensitizer. Likewise the yield of totalproducts boiling below 400 F., with 1.0% by weight of d-bromocamphor was33.9, whereas it was 16.7% without any sensitizer.

Another series of runs was made using Pennsylvania gas-oil as chargingstock under a pressure of 500 pounds per square inch in which thetemperature was kept at approximately 887 F. during each run. Theresults on these runs are tabulated in Table II.

In practicing the invention, the halogenated Table II cyclic terpenes,camphors, or derivatives thereof. R N may be mixed with the hydrocarbonsto be 2 3 4 5 6 charged to the process prior to entrance thereof R t a Fthe rem! zone or the miller may be 5 pfttr'.f$7s.:..1::::::::::: 333 583233 $5 flash-injected directly into the reaction zone, hm sglbalhr 6.8006.2 361 can sets case after heating sumclenuy to either melt vapor"fiifiiiitfii; wfl'fier'rifi 025 022 4 905 ize the sensitizer. Whereflash-injection is pracgiquid products, 1m /hr 6.453 6.711 6.532 0.5116.588 tlced, care should be exercised n to heat the 033: .a.::::::::::"333 313i? i1??? i333? Hi3 sensitizer above its decomposition temperatureMaterlal'balame 0.986 1.024 0.997 0.992 1.001 prior to its injectioninto the reaction zone. hm "mm-Mien In order to demonstrate theeffectiveness of 1*" m w 'wo g ggl n rs l l fi Seuss l l 1 gr's andlighter 2.6 3.0 2.8 2.3 2.6 me e g ennsy va a gas-o as c arg ng 4' 0.81.0 0.8 0. 0.8

i i i, 1 r. stock in a continuous laboratory cracking opera- $31, 3 mud2.3 3} tion. The runs were carried out at a tempera- J n a-agav ioozr 7.9 1 .1 71. gig 13.2 ture of approximately 977 F. and at atmospheric g ggg ft m gi R y 2 pressure. In three of the runs d-bromocamphor gg l fl60.8 59.7 00.0 was used as sensitizer in diflerent amounts, A flon)H5'cc TEL/ga1' r 63.7 6&5 6&2 blank run was made in order to form a basisof gt g fi s i g g fi; 64 8 66 4 66 4 66 2 comparison and a run was madewith bromine in f+ 1% b g g fi g f ion cc. ga 6 .6 '1. order to show theeffectiveness of d bromocam octane No. (1004000 F w I phorasasensltizer. tion)+3.0 cc. TEL/gal.. 12.1 73.6 was 73.4

The results of the several runs are given in the following table: Id-Bromo camphor.

Table I Run No. 24-6 Run No. 28-G Run No. 21-0 Run No 22-G Run No. 23-6'Tcmperature,F s17 971 919 971 979.

Premurefin atm atm atm. Charge gins. 165.2 164.8 164.0. Sensitlzerd-bromo-camphor d-bromo-camphor d-bromo-camphor (1.0% by wt). (0.6% bywt.). (0.1% by wt). Liquid Products, gins/hr 145.2 148.4- 152.0. GasProducts, gins/hr 19.0 15.7 12.1. Liguir' z it rigucts below 400 F., For

-81! 0 urge:

Vol Wt Liquid Products above 400 F., Per

Cent 01 Charge:

Vol t Gas Produced, Wt. Per Cent of Charge. Specific Gravity of Gas Itis apparent from Table II that even when 4 as little as .05% by weightof d-bromocamphor was used, an increase of approximately 18% in yield ofliquid hydrocarbons boiling up to 400 F. was obtained. It is alsoevident from Table II that the liquid product boiling within thegasoline boiling range obtained, using d-bromocamphor as sensitizer, ishigher than the octane number of the gasoline obtained withoutsensitizer. Thus, not only do sensitizers within the scope of theinvention produce more gasoline than can be produced without sensitizerunder similar cracking conditions, but they also produce gasoline ofhigher octane rating.

Although my invention is applicable to all known types of therma1hydrocarbon cracking processes, including catalytic and purely thermal,it is particularly adapted for use in connection .with thermaloperations in which no solid catalyst is used. The invention may be usedin present types of thermal cracking processes and apparatus withoutmodifying such processes or the apparatus in which they are conducted,except to the extent necessary to provide for the introduction of thesensitizer at some point in the operation prior to the time the productsleave the reaction zone.

It is to be understood that my invention is directed to the use ofbrominated terpenes and camphor type compounds, regardless of whethergroups or elements other than bromine are attached to the terpene orcamphor rings. and is more particularly directed to brominatedpolycyclic terpenes, camphors and their derivatives.

It is claimed:

1. The method-of cracking hydrocarbons comprising subjecting saidhydrocarbons to suitable cracking conditions in the presence of a smallamount of a substance selected from the group consisting ofbromine-containing terpenes, camphors, their esters and ethers, andamino, nitro, alkyl, aryl, or aralkyl derivatives thereof.

2. The method of cracking hydrocarbons comprising subjecting saidhydrocarbons to temperatures of approximately 650 to 2000 F. in thepresence of a small amount of a substance selected from the groupconsisting of bromine-containing terpenes, camphors, their esters andethers, and amino, nitro, alkyl, aryl or aralkyl derivatives thereof.

3. The method of cracking hydrocarbons containing a major proportion ofpropane comprising, subjecting said hydrocarbons to temperatures ofapproximately 650 to 2000 F. in the presence of a small amount of asubstance select ed from the group consisting of bromine-containingterpenes and camphors, their esters, ethers, and amino, nitro, alkyl,aryl, or aralkyl derivatives thereof.

4. The method of cracking hydrocarbons boiling above the gasolineboiling range comprising, subjecting said hydrocarbons to temperaturesof approximately 650 to 2000 F. in the presence of a small amount of asusbtance selected from the group consisting of bromine-containingterpenes and camphcrs, their esters, ethers, and amino, nitro, alkyl,aryl, or aralkyl derivatives thereof.

5. The method of cracking higher boiling hydrocarbon oils tohydrocarbons within the gasoline boiling range comprising subjectingsaid oils to cracking at temperatures of approximately 650 to 1200 F. inthe presence of approximately .05 to 3% by weight of a substanceselected from the group consisting of bromine-containing terpenes,camphors, their esters and ethers, and amino, nitro, alkyl, aryl, oraralkyl derivatives thereof.

6. The method of cracking higher boiling hydrocarbon oils tohydrocarbons within the gasoline boiling range comprising, subjectingsaid oils to cracking at temperatures of approximately 650 to 1200 F. inthe presence of approximately 0.05 to 3 per cent by weight 01 abromo-camphor.

7. The method of cracking higher boiling hydrocarbon oils tohydrocarbons within the caseline boiling range comprising, subjectingsaid oils to temperatures of approximately 650 to 1200 F. in thepresence oi approximately 0.05 to 3 per cent by weight ord-bromocamphor.

8. The method of cracking higher boiling hydrocarbon oils tohydrocarbons within the gasoline boiling range comprising, subjectingsaid oils to temperatures of approximately 650 to 1200 F. in thepresence of approximately 0.05 to 3 per cent by weight ofdibromocamphor.

9. The method of cracking hydrocarbon oil boiling above the gasolinerange comprising subjecting said oil to a temperature of approximately977 F. in the presence of approximately .1 to 1% by weight ofd-bromocamphor for a period of time suitable for cracking a substantialportion of said oil to gasoline boiling hydrocarbons.

10. The method of cracking hydrocarbons comprising, subjecting saidhydrocarbons to suitable cracking conditions in the presence of a smallamount at a bromine-containing cyclic terpene.

11. The method of cracking hydrocarbons comprising. subjecting saidhydrocarbons to temperatures of approximately 650 to 2000 F. in thepresence, of a small amount of a bromine-containing cyclic terpene. h12. The method of cracking higher boiling hydrocarbon oils tohydrocarbons within the gasoline boiling range comprising, subjectingsaid oils to temperatures of approximately 650 to 1200 F. in thepresence of approximately 0.05 to 3 per cent by weight of a bicyclicterpene containing at least one bromine-atom in the molecule.

13. The method of cracking hydrocarbons comprising, subjecting saidhydrocarbons to suitable cracking conditions in the presence of a smallamount of a bromine-containing camphor.

14. The method of cracking hydrocarbons comprising, subjecting saidhydrocarbons to suitable cracking conditions in the presence of a smallamount of a bromine-containing polycyclic ter-' 'pene.

HILLIS O. FOLKINS.

REFERENCES CITED The following references are bi record in the file ofthis patent:

UNITED STATES PATENTS

